CN105255061A - Environment-friendly soft PVC plasticizer - Google Patents
Environment-friendly soft PVC plasticizer Download PDFInfo
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- CN105255061A CN105255061A CN201510783637.7A CN201510783637A CN105255061A CN 105255061 A CN105255061 A CN 105255061A CN 201510783637 A CN201510783637 A CN 201510783637A CN 105255061 A CN105255061 A CN 105255061A
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- softening agent
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Abstract
The invention relates to the technical field of functional polymer material preparing and modifying, in particular to an environment-friendly soft PVC plasticizer. The plasticizer is prepared from, by weight, 60 parts to 70 parts of cage-type organosilicon hybridization star-type polyester, 10 parts to 20 parts of fatty acid methyl ester, 20 parts to 25 parts of epoxidized fatty acid methyl ester, 5 parts to 8 parts of benzoic acid, 5 parts to 8 parts of ethanediol, 3 parts to 5 parts of carbamide, 5 parts to 8 parts of dissolubility polyving akohol and 2 parts to 6 parts of epoxidized soybean oil. The plasticizer is nontoxic and environmentally friendly, and has the advantages of being free of volatility and mobility and good in PVC compatibility and durability.
Description
Technical field
The present invention relates to the technical field of functional high molecule material preparation and modification, be specifically related to a kind of environmentally friendly flexible PVC softening agent.
Background technology
Softening agent refers to the plasticity-having and increase plastics, improves the mobility of plastics resin when machine-shaping, and makes plastics have flexible organic substance.Softening agent is some high boiling points normally, be difficult to the thick liquid that volatilizees or the solid of LMP, general requirement softening agent is colourless, nontoxic, odorless, cold-resistant, heat-resisting, volatility and transport property be little, and chemical stability is good, cheap and easy to get.Softening agent can weaken the Van der Waals force between plastic polymer molecule, increase the movability of polymer molecular chain, the crystallinity of polymer molecular chain is reduced, the plasticity of polymkeric substance is enhanced, thus the hardness of reduction polymkeric substance, softening temperature and embrittlement temperature, improve the circumnutating property of plastics, extensibility and snappiness.
Softening agent is mainly used in polyvinyl chloride resin, therefore the development of softening agent and the development of polyvinyl chloride industrial closely bound up.And at present due to the fast development of plastics industry, the requirement of softening agent also gets more and more.Meanwhile, softening agent produced problem also continues to bring out, " Taiwan softening agent " disturbance particularly in succession occurred and " Jiu Gui Jiu " white wine softening agent disturbance, cause the public opinion that people use softening agent security, the environmental pollution that softening agent causes and the growing interest causing people is started to the healthy potential problem of the mankind, because softening agent can move out under certain condition from PVC product, this shortcoming makes softening agent become the target of everyone.The Application Areas of phthalic ester plasticizer is the most extensive, consumption is maximum, if but this softening agent is used in PVC product, migration out can have destruction to the endocrine system of human body, the change of Hormone system can be caused and cause the problem of reproductive development, especially larger detrimentally affect being also existed to growing of infant.Therefore the softening agent researching and developing some asepsis environment-protectings becomes the focus of people's concern gradually.
Wherein, polyester plasticizer belongs to the category of superpolymer, is characterized in that the volume of molecule is greater than the volume of monomeric plastizer agent molecule, and relative molecular mass is comparatively large, makes the agent of various plastic product post-plasticization not easily therefrom move out when adding in polyvinyl chloride resin as softening agent.Therefore, the character that polyester plasticizer can make PVC plastic goods have some special, these special character determine plastics test piece prepared therefrom and have excellent application performance, as resistance to migration is strong, solvent resistant effect is excellent, weathering resistance is strong.Polyester plasticizer is specially adapted to some plastics used for a long time and sensitive article fields, as plastics such as plastics, refrigerator plastics, doughnut, packaging material for food, straw, medicine equipment, cosmetic package, blood plasma storage bags in electric wire, automobile.When plastics need and organic liquid Long Term Contact when keeping intrinsic physico-chemical attributes, polyester plasticizer perfectly can play the advantage of the strong and excellent durability of its resistance to migration, so polyester plasticizer just develops rapidly with himself advantage, purposes is increasingly extensive, output and consumption increase year by year, have a extensive future.
Summary of the invention
The object of the invention is to solve defect of the prior art, a kind of nontoxic, environmental protection is provided, service requirements, flexible PVC softening agent with short production cycle can be met, possess the application performances such as resistance to migration, solvent resistant effect, weathering resistance simultaneously.
To achieve these goals, a kind of environmentally friendly flexible PVC softening agent, counted by weight by following component and form:
The star-like polyester of cage modle organic-silicon hybridization 60 ~ 70 parts;
Fatty acid methyl ester 10 ~ 20 parts;
Epoxy aliphatic acid methyl ester 20 ~ 25 parts;
5 ~ 8 parts, phenylformic acid;
Ethylene glycol 5 ~ 8 parts;
Carbonyl diamine 3 ~ 5 parts;
Soluble polyvinyl alcohol 5 ~ 8 parts;
Epoxy soybean oil 2-6 part.
Further, the described star-like polyester of cage modle organic-silicon hybridization is prepared by following method: (1) ricinolic acid carries out pyrolysis oxidization, Pd/C catalytic hydrogenation reaction by ozone oxidation successively, obtains the mix products of nonyl alcohol acid and 1,3-dihydroxyl nonanediol; (2) there is ester hydrolysis reaction in the drift angle group of prestox acryloxypropyl cage-type silsesquioxane in aqueous sulfuric acid, and stirring and refluxing reaction 4h, obtains eight propyl alcohol base cage-type silsesquioxanes; (3) the eight propyl alcohol base cage-type silsesquioxanes that mix products step (1) obtained and step (2) obtain, mix in mass ratio with dimeracid, obtained mixed solution; Catalyst for esterification reaction heteropolyacid PW is added in mixed solution
12/ SiO
2and dewatering agent DCC, back flow reaction 4h, obtain the star-like polyester of cage modle organic-silicon hybridization.
Preferably, in described step (3), the mass ratio of mix products, eight propyl alcohol base cage-type silsesquioxanes and dimeracid is 80:10:10.
Beneficial effect of the present invention: the PVC softening agent that the present invention announces is nontoxic, environmental protection, has the feature of non-volatility, nonmigratory, the resistance to persistence good, good with PVC consistency.
Accompanying drawing explanation
Fig. 1 is the star-like polyester molecule structure iron of cage modle organic-silicon hybridization;
Fig. 2 is dimeracid molecular structure.
Embodiment
In conjunction with Fig. 1-2, embodiments of the present invention are elaborated.It is emphasized that following explanation is only exemplary, instead of in order to limit the scope of the invention and apply.
Embodiment 1
A kind of environmentally friendly flexible PVC softening agent, counted by weight by following component and form:
The star-like polyester of cage modle organic-silicon hybridization 60 parts;
Fatty acid methyl ester 20 parts;
Epoxy aliphatic acid methyl ester 25 parts;
5 parts, phenylformic acid;
Ethylene glycol 5 parts;
Carbonyl diamine 4 parts;
Soluble polyvinyl alcohol 7 parts;
Epoxy soybean oil 4 parts.
The described star-like polyester of cage modle organic-silicon hybridization is prepared by following method: (1) ricinolic acid carries out pyrolysis oxidization, Pd/C catalytic hydrogenation reaction by ozone oxidation successively, obtains the mix products of nonyl alcohol acid and 1,3-dihydroxyl nonanediol; (2) there is ester hydrolysis reaction in the drift angle group of prestox acryloxypropyl cage-type silsesquioxane in aqueous sulfuric acid, and stirring and refluxing reaction 4h, obtains eight propyl alcohol base cage-type silsesquioxanes; (3) the eight propyl alcohol base cage-type silsesquioxanes that mix products step (1) obtained and step (2) obtain, with dimeracid in mass ratio for 80:10:10 mixes, obtained mixed solution; Catalyst for esterification reaction heteropolyacid PW is added in mixed solution
12/ SiO
2and dewatering agent DCC, back flow reaction 4h, obtain the star-like polyester of cage modle organic-silicon hybridization.
After adding above-mentioned softening agent, the PVC plastic time is 1.4 minutes, and plasticizing is easier to, and plasticizing capacity is good, and plasticizing efficiency is high.
Embodiment 2
The present embodiment is identical with the moiety of embodiment 1, and difference is the environmentally friendly flexible PVC softening agent of described one, is counted by weight form by following component:
The star-like polyester of cage modle organic-silicon hybridization 65 parts;
Fatty acid methyl ester 20 parts;
Epoxy aliphatic acid methyl ester 25 parts;
5 parts, phenylformic acid;
Ethylene glycol 5 parts;
Carbonyl diamine 5 parts;
Soluble polyvinyl alcohol 7 parts;
Epoxy soybean oil 4 parts.
After adding above-mentioned softening agent, the PVC plastic time is 1.1 minutes, and easily, plasticizing capacity is good, and plasticizing efficiency is high in plasticizing.
Embodiment 3
The present embodiment is identical with the moiety of embodiment 1, and difference is the environmentally friendly flexible PVC softening agent of described one, is counted by weight form by following component:
The star-like polyester of cage modle organic-silicon hybridization 70 parts;
Fatty acid methyl ester 20 parts;
Epoxy aliphatic acid methyl ester 25 parts;
5 parts, phenylformic acid;
Ethylene glycol 5 parts;
Carbonyl diamine 4 parts;
Soluble polyvinyl alcohol 7 parts;
Epoxy soybean oil 4 parts.
After adding above-mentioned softening agent, the PVC plastic time is 1.0 minutes, and easily, plasticizing capacity is good, and plasticizing efficiency is high in plasticizing.
Embodiment 4
The present embodiment is identical with the moiety of embodiment 1, and difference is the environmentally friendly flexible PVC softening agent of described one, is counted by weight form by following component:
The star-like polyester of cage modle organic-silicon hybridization 70 parts;
Fatty acid methyl ester 20 parts;
Epoxy aliphatic acid methyl ester 25 parts;
5 parts, phenylformic acid;
Ethylene glycol 6 parts;
Carbonyl diamine 4 parts;
Soluble polyvinyl alcohol 6 parts;
Epoxy soybean oil 5 parts.
After adding above-mentioned softening agent, the PVC plastic time is 1.3 minutes, and plasticizing is easier to, and plasticizing capacity is good, and plasticizing efficiency is high.
Embodiment 5
The present embodiment is identical with the moiety of embodiment 1, and difference is the environmentally friendly flexible PVC softening agent of described one, is counted by weight form by following component:
The star-like polyester of cage modle organic-silicon hybridization 60 parts;
Fatty acid methyl ester 20 parts;
Epoxy aliphatic acid methyl ester 25 parts;
8 parts, phenylformic acid;
Ethylene glycol 8 parts;
Carbonyl diamine 5 parts;
Soluble polyvinyl alcohol 8 parts;
Epoxy soybean oil 6 parts.
After adding above-mentioned softening agent, the PVC plastic time is 1.5 minutes, and plasticizing is easier to, and plasticizing capacity is better, and plasticizing efficiency is higher.
Embodiment 5
The present embodiment is identical with the moiety of embodiment 1, and difference is the environmentally friendly flexible PVC softening agent of described one, is counted by weight form by following component:
The star-like polyester of cage modle organic-silicon hybridization 60 parts;
Fatty acid methyl ester 10 parts;
Epoxy aliphatic acid methyl ester 20 parts;
5 parts, phenylformic acid;
Ethylene glycol 5 parts;
Carbonyl diamine 3 parts;
Soluble polyvinyl alcohol 5 parts;
Epoxy soybean oil 2 parts.
After adding above-mentioned softening agent, the PVC plastic time is 1.8 minutes, and plasticizing is easier to, and plasticizing capacity is better, and plasticizing efficiency is higher.
Last it is noted that obviously, above-described embodiment is only for example of the present invention is clearly described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of amplifying out or variation be still among protection scope of the present invention.
Claims (3)
1. an environmentally friendly flexible PVC softening agent, is characterized in that, is counted by weight form by following component:
The star-like polyester of cage modle organic-silicon hybridization 60 ~ 70 parts;
Fatty acid methyl ester 10 ~ 20 parts;
Epoxy aliphatic acid methyl ester 20 ~ 25 parts;
5 ~ 8 parts, phenylformic acid;
Ethylene glycol 5 ~ 8 parts;
Carbonyl diamine 3 ~ 5 parts;
Soluble polyvinyl alcohol 5 ~ 8 parts;
Epoxy soybean oil 2-6 part.
2. the environmentally friendly flexible PVC softening agent of one according to claim 1, it is characterized in that, the described star-like polyester of cage modle organic-silicon hybridization is prepared by following method: (1) ricinolic acid carries out pyrolysis oxidization, Pd/C catalytic hydrogenation reaction by ozone oxidation successively, obtain the mix products of nonyl alcohol acid and 1,3-dihydroxyl nonanediol; (2) there is ester hydrolysis reaction in the drift angle group of prestox acryloxypropyl cage-type silsesquioxane in aqueous sulfuric acid, and stirring and refluxing reaction 4h, obtains eight propyl alcohol base cage-type silsesquioxanes; (3) the eight propyl alcohol base cage-type silsesquioxanes that mix products step (1) obtained and step (2) obtain, mix in mass ratio with dimeracid, obtained mixed solution; Catalyst for esterification reaction heteropolyacid PW is added in mixed solution
12/ SiO
2and dewatering agent DCC, back flow reaction 4h, obtain the star-like polyester of cage modle organic-silicon hybridization.
3. the environmentally friendly flexible PVC softening agent of one according to claim 2, is characterized in that, in described step (3), the mass ratio of mix products, eight propyl alcohol base cage-type silsesquioxanes and dimeracid is 80:10:10.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510783637.7A CN105255061B (en) | 2015-11-16 | 2015-11-16 | A kind of environmentally friendly flexible PVC plasticizer |
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| CN201510783637.7A CN105255061B (en) | 2015-11-16 | 2015-11-16 | A kind of environmentally friendly flexible PVC plasticizer |
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| CN105255061A true CN105255061A (en) | 2016-01-20 |
| CN105255061B CN105255061B (en) | 2016-08-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200957A (en) * | 2017-06-06 | 2017-09-26 | 滁州市宏源喷涂有限公司 | A kind of method of epoxy aliphatic acid methyl ester resistance to migration in raising flexible PVC |
| CN107641325A (en) * | 2017-09-05 | 2018-01-30 | 四川大学 | Non-migrating type POSS grafting age resistor and preparation method thereof |
| CN108047491A (en) * | 2018-01-25 | 2018-05-18 | 广东达华生态科技有限公司 | A kind of new PVC plasticizer and preparation method thereof |
| CN108659386A (en) * | 2018-05-04 | 2018-10-16 | 广东祺龙科技有限公司 | A kind of robot drag chain PVC modified materials and preparation method thereof |
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| CN1370790A (en) * | 2000-12-07 | 2002-09-25 | 郭承烨 | Aliphatic polyester compound with highly branched structure as plasticizer for polyvinyl chloride and flexible polyvinyl chloride blend with the compound |
| CN101302158A (en) * | 2008-06-06 | 2008-11-12 | 江南大学 | Method for synthesizing PVC plasticiser by reclaiming waste polyester |
| WO2008137209A1 (en) * | 2007-03-19 | 2008-11-13 | Hybrid Plastics, Inc. | Fluorinated poss as alloying agents in nonfluorinated polymers |
| CN103804669A (en) * | 2014-02-28 | 2014-05-21 | 江南大学 | Method for preparing caster oil-based polyester serving as PVC (Polyvinyl Chloride) plasticizer |
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2015
- 2015-11-16 CN CN201510783637.7A patent/CN105255061B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370790A (en) * | 2000-12-07 | 2002-09-25 | 郭承烨 | Aliphatic polyester compound with highly branched structure as plasticizer for polyvinyl chloride and flexible polyvinyl chloride blend with the compound |
| WO2008137209A1 (en) * | 2007-03-19 | 2008-11-13 | Hybrid Plastics, Inc. | Fluorinated poss as alloying agents in nonfluorinated polymers |
| CN101302158A (en) * | 2008-06-06 | 2008-11-12 | 江南大学 | Method for synthesizing PVC plasticiser by reclaiming waste polyester |
| CN103804669A (en) * | 2014-02-28 | 2014-05-21 | 江南大学 | Method for preparing caster oil-based polyester serving as PVC (Polyvinyl Chloride) plasticizer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200957A (en) * | 2017-06-06 | 2017-09-26 | 滁州市宏源喷涂有限公司 | A kind of method of epoxy aliphatic acid methyl ester resistance to migration in raising flexible PVC |
| CN107641325A (en) * | 2017-09-05 | 2018-01-30 | 四川大学 | Non-migrating type POSS grafting age resistor and preparation method thereof |
| CN107641325B (en) * | 2017-09-05 | 2020-05-12 | 四川大学 | Non-migration POSS grafted antioxidant and preparation method thereof |
| CN108047491A (en) * | 2018-01-25 | 2018-05-18 | 广东达华生态科技有限公司 | A kind of new PVC plasticizer and preparation method thereof |
| CN108659386A (en) * | 2018-05-04 | 2018-10-16 | 广东祺龙科技有限公司 | A kind of robot drag chain PVC modified materials and preparation method thereof |
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| CN105255061B (en) | 2016-08-17 |
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Address after: 515559 Guangdong County of Jiedong province Jieyang Paotai town Kengzi in Pai Patentee after: Guangdong Dahua ecological science and Technology Co Ltd Address before: 515559 Guangdong County of Jiedong province Jieyang Paotai town Kengzi in Pai Patentee before: GUANGDONG DAHUA WATER SAVING TECHNOLOGY CO., LTD. |